Anti-stripping agents



United States Patent This application is a continuation of our application Serial No. 115,880, filed on June 9, 1961, which is a division of application Serial No. 47,387, filed on August 4,

1960, now withdrawn as an application, and is co-pending with application Serial No. 458,373, filed on May 24, 1965, as a division of said application Serial No. 47,387, and is co-pending with each of the following applications, Serial Numbers:

Serial No. Filing Date Title June 9, 1961 Fuel Compositions. June 9,1961 Process of Preventing Scale. June 9, 1961 Process of Breaking Emulsions. June 9, 1961 Lubrication Composition.

June 9, 1981 Preventing Corrosion.

June 9, 1961 Inhibiting Foam.

June 9,1961 Flotation Process. June 9,1961 Drilling Fluids. June 9, 1961 Treatment of Oil Wells.

Applications Serial Nos. 47,387, 115,879, and 115,880 are now abandoned.

This invention relate to polya-lkyleneimines and to derivatives thereof. More particularly, this invention relates to polyethyleneimine and to polyethyleneimine derivatives containing various groups, such as the oxyalkylated, acylated, alkylated, carbonylated, olefinated, etc., derivatives thereof, prepared by introducing such groups individually, alternately, in combination, etc., including for example, derivatives prepared by varying the order of adding such groups, by increasing the number and order of adding such groups, and the like.

This invention also relates to methods of using these products, which have an unexpectedly broad spectrum of uses, for example, as demulsifiers for water-in-oil emulsions; as demulsifiers for oil-in-water emulsions; as corrosion inhibitors; as fuel oil additives for gasoline, diesel fuel, jet fuel, and the like; as lubricating oil additives; as scale preventatives; as chelating agents or to form chelates which are themselves useful, for example, as antioxidants, gasoline stabilizers, fungicides, etc.; as flotation agents, for example, as flotation collection agents; as asphalt additives or anti-stripping agents for asphalt-mineral aggregate compositions; as additives for compositions useful in acidizing calcareous strata of oil wells; as additives for treating Water used in the secondary recovery of oil and in disposal wells; as additives used in treating oil-well strata in primary oil recovery to enhance the flow of oil; as emulsifiers for both oil-in-water and water-in-oil emulsions; as additives for slushing oils; as additives for cutting oils; as additives for oil to prevent emulsification during transport; as additives for drilling muds; as agents useful in removing mud sheaths from newly drilled wells; as dehazing or fog-inhibiting agents for fuels; as additives for preparing sand or mineral slurries useful in treating oil wells to enhance the recovery of oil; as agents for producing polymeric emulsions useful in preparing Watervapor impermeable paper board; as agents in paraflin solvents; as agents in preparing thickened silica aerogel lubricants; as gasoline additives to remove copper therefrom; as deicing and anti-stalling agents for gasoline; as antiseptic, preservative, bactericidal, bacteriostatic, germicidal, fungicidal agents; as agent for the textile industry, for example, as mercerizing assistants, as wetting agents,

3,259,513 Patented July 5, 1966 'ice as rewetting agents, as dispersing agents, as detergents, as penetrating agents, as softening agents, as dyeing ESSlS. tants, a anti-static agents, and the like; as additives for rubber latices; as entraining agents for concrete and cements; as anti-static agents for rugs, floors, upholstery, plastic and Wax polishes, textiles, etc.; as detergents useful in metal cleaners, in floor oils, in dry cleaning, in general cleaning, and the like; as agents useful in leather processes such as in flat liquoring, pickling, acid degrea-sing, dye fixing, and the like; as agents in metal picklingqas additives in paints for improved adhesion of primers, in preventing water-spotting in lacquer; as anti-Skinners for pigment flushing, grinding and dispersing, as antifeathering agents in ink; as agents in the preparation of wood pulp and pulp slurries, as emulsifiers for insecticidal compositions and agricultural sprays such as DDT, Z4D (Toxa phene), chlordane, nicotine sulfate, hexachloracyclohexane, and the like; as agents useful in building materials, for example, in the water repellent treatment of plaster, concrete, cement, roofing materials, floor sealers; as additives in bonding agents for various insulating building materials; and the like.

Polyalkyleneimine employed in this invention include high molecular Weight polyethyleneimine, i.e., polymers of ethyleneimine,

CHz-CH:

or substituted products thereof:

CRz-C Rz N H I etc.

wherein R, R and R" are hydrogen or a substituted group, for example a hydrocarbon group such as alkyl, cycloalkyl, aryl, aralkyl, alkaryl, etc., but preferably hydrogen or alkyl.

Thus, polyethyleneimine is polymerized, substituted or an unsubstituted, 1,2-alkyleneimine. Although polyethyleneimine is the preferred embodiment, other illustrative examples include, for example,

' CHI-CH3 0 H2 1,2-propy1eneim1ne CHI-G 2H5 2,3-buty1eneimine C Ha C-octadecylethyleneimine A preferred class of polymerized 1,2 alkyleneimines include those derived from polymerizing RCHROH wherein R and R are hydrogen or an alkyl radical, the latter being the same or different. Of the substituted ethyleneimines, propyleneimines are preferred.

The polyethyleneimines useful herein have molecular weights of, for example, at least 800, for example from 800 to 100,000 or higher, but preferably 20,000 to 75,000 or higher. There is no upper limit to the molecular weight of the polymer employed herein and molecular weights of 200,000, 500,000 or 1,000,000 or more can be employed.

The optimum molecular weight will depend on the particular derivative, the particular use, etc.

Although these products are generally prepared by polymerizing 1,2 alkyleneimines, they may also be prepared by other known methods, for example, by decarboxylating 2-oxazolidine as. described in 2,806,839, etc. Commercial examples of these compounds are available, for example, those sold in a 50% by weight aqueous solution having a molecular weight of 3040,000. Propyleneimine is also commercially available and suitable polymers can be prepared from. this material.

For convenience and simplicity, this invention will be illustrated by employing olyethyleneimine.

Polyethyleneimine is a well known polymer whose preparation from ethyleneimine is described in US. Patent 2,182,306 and elsewhere. For convenience in polymerizing and handling, the polymer is generally prepared as an aqueous solution. Water can be removed, if desired, by distilling the Water therefrom or by azeotroping the water therefrom in the presence of a hydrocarbon, such as xylene, and using the solution and/or suspension obtained thereby for further reaction or use. The following polyethyleneimines of the molecular weights indicated are employed herein to illustrate this invention.

Approx. mol. wgt. range 800-1000 4000-6000 10,500-12,500 1s,000 22,000

Polymer designation: v

Polyethyleneimine 900 Polyethyleneimine 5,000 Polyethyleneimine 11,500 Polyethyleneimine 20,000

ACYLATION A wide variety of acylating agents can be employed. Acylation is carried out under dehydrating conditions, i.e., water is removed. Any of the well-known methods of acylation can be employed. For example, heat alone, heat and reduced pressure, heat in combination with an azeotroping agent, etc., areall satisfactory.

The temperature at which reaction between the acylating agent and polyethyleneimine is effected is not too critical a factor. Since the reactions involved appear to be an amide-formation reaction and a condensation reaction, the general temperature conditions for such reactions, which are well known to those skilled in the art, are applicable.

Acylation is conducted ata temperature sufficiently high to eliminate waterand below the pyrolytic point of the reactants and the reaction products. In general, the reaction is carried out at a temperature of from 120 to 280 C., but preferably at 140 to 200 C.

The product formed on acylation will vary with the particular conditions employed. First the salt, then the amide is formed. If, however, after forming the amide at a temperature between 250 C., but usually not above 200 C., one heats such products at a higher range, approximately 250280 C., or higher, possibly up to 300 C. for a suitable period of time, for example, 1-2 hours or longer, one can in many cases recover a second mole of water for each mole of carboxylic acid group employed, the first mole of water being evolved during amidification. The product formed in such cases contains a cyclic amidine ring, such as an imidazoline or a tetrahydropyrimidine ring. Infrared analysis is a convenient method of determining the presence of these groups.

Water is formed as a by-product of the reaction between the acylating agent and polyethyleneimine. In order to facilitate the removal of this water, to effect a more complete reaction in accordance with the principle of Le Chatelier, a hydrocarbon solvent which forms an azeotropic mixture with water can be added to the reaction mixture. Heating is continued with the liquid reaction mixture at the preferred reaction temperature, until the removal of water by azeotropic distillation has substantially ceased. In general, any hydrocarbon solvent which forms an azeotropic mixture with water can be used. It is preferred, however, to use an aromatic hydrocarbon solvent of the benzene series. Non-limiting examples of the preferred solvent are benzene, toluene, and xylene. The amount of solvent used as a variable and non-critical factor. It is dependent on the size of the reaction vessel and the reaction temperature selected. Accordingly, a suflicient amount of solvent must be used to support the azeotropic distillation, but a large excess must be avoided since the reaction temperature will be lowered thereby. Water produced by the reaction can also be removed by operating under reduced pressure. When operating with a reaction vessel equipped with a reflux condenser providecl with a water takeofi trap, sufiicient reduced pressure can be achieved by applying a slight vacuum to the upper end of the condenser. The pressure inside the system is usually reduced to between about 50 and about 300 millimeters. If desired, the Water can be removed also by distillation, while operating under relatively high temperature conditions.

The time of reaction between the acylating agent and olyethyleneimine is dependent on the weight of the charge, the reaction temperature selected, and the means employed for removing the water from the reaction mixture. In practice, the reaction is continued until the formation of water has substantially ceased. In general, the time of reaction will vary between about 4 hours and about ten hours.

Although a wide variety of carboxylic acids produce excellent products, carboxylic acids having more than six carbon atoms and less than 40 carbon atoms but preferably 830 carbon atoms give most advantageous products. The most common examples include the detergent fonning acids, i.e., those acids which combine with alkalies to produce soap or soap-like bodies. The detergent-forming acids, in turn, include naturally-occurring fatty-acids, resin acids, such as abietic acid, naturallyoccurring petroleum acids, such as naphthenic acids, and carboxy acids, produced by the oxidation of petroleum. As will be subsequently indicated, there are other acids which have somewhat similar characteristics and are derived from somewhat different sources and are different in structure, but can be included in the broad generic term previously indicated.

Suitable acids include straight chain and branched chain, saturated and unsaturated, aliphatic, alicyclic, fatty, aromatic, hydroaromatic, and aralkyl acids, etc.

Examples of saturated aliphatic monocarboxylic acids are acetic, propionic, butyric, valeric, caproic, heptanoic, caprylic, nonanoic, capric, undecanoic, lauric, tridecanoic,

acids, the hexenoic acids, for example, hydrosorbic acid,

the heptenoic acids, the octenoic acids, the nonenoic acids, the decenoic acids, for example, obtusilic acid, the undecenoic acids, the dodencenoic acids, for example, lauroleic, linderic, etc., the tridecenoic acids, the tetradecenoic acids, for example, myristoleic acid, the pentadecenoic acids, the hexadecenoic acids, for example, palmitoleic acid, the heptadecenoic acids, the octodccenoic acids, for

example, petrosilenic acid, oleic acid, elardic acid, the nonadecenoic acids, for example, the eicosenoic acids, the docosenoic acids, for example, erucic acid, brassidic acid, cetoleic acid, the tetradosenic acids, and the like.

Examples of dienoic acids are the pentadienoic acids, the hexadienoic acids, for example, sorbic acid, the octadienoic acids, for example, linoleic, and the like.

Examples of the trienoic acids are the octadecatrienoic acids, for example, linolenic acid, eleostearic acid, pseudoeleostearic acid, and the like.

Carboxylic :acids containing functional groups such as hydroxy groups can be employed. Hydroxy acids, particularly the alpha hydroxy acids include glycolic acid, lactic acid, the hydroxyvaleric acids, the hydroxy caproic acids, the hydroxy-heptanoic acids, the hydroxy caprylic acids, the hydroxynonanoic acids, the hydroxycapric acids, the hydroxydecanoic acids, the hydroxy lauric acids, the hydroxy tridecanoic acids, the hydroxy-myristic acids, the hydroxypentadecanoic acids, the hydroxy-palmitic acids, the hydroxyhexadecanoic acids, the .hydroxyheptadecanoic acids, the hydroxy stearic acids, the hydroxyoctadecenoic acids, for example, ricinoleic acid, ricinelardic acid, hydroxyoctadecynoic acids, for example, ricinstearolic acid, the hydroxyeicosanoic acids, for example, hydroxyarachidic acid, the hydroxydocosanoic acids, for example, hydroxybehenic acid, and the like.

Examples of acetylated hydroxyacids are ricinoleyl lactic acid, acetyl ricinoleic acid, chloroacetyl ricinoleic acid, and the like.

Examples of the cyclic aliphatic carboxylic acids are those found in petroleum called naphthenic acids, hydrocarbic and chaumoogric acids, cyclopentane carboxylic acids, cyclohexanecarboxylic acid, campholic acid, fenchlolic acids, and the like.

Examples of aromatic monocarboxylic acids are ben- Zoic acid, substituted benzoic acids, for example, the toluic acids, the xyleneic acids, alkoxy benzoic acid, phenyl benzoic acid, naphthalene carboxylic acid, and the like.

Mixed higher fatty acids derived from animal or vegetable sources, for example, lard, cocoanut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oil, and other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils are advantageously employed. Fatty and similar acids include those derived from various waxes, such as beeswax, spermaceti, montan Wax, japan wax, coccerin and carnauba wax. Such acids include carnaubic acid, cerotic acid, lacceric acid, montanic acid, psyllastearic acid, etc. One may also employ higher molecular weight carboxylic acids derived by oxidation and other methods, such as from paraflin wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acids, such as hexahydrobenzoic acid, hydrogenated naphthoic, hydrogenated carboxy diphenyl, naphthenic, and abietic acid; Twitchell fatty acids, carboxydiphenyl pyridine carboxylic acid, blown oils, blown oil fatty acids and the like.

Other suitable acids include phenylstearic acid, benzoylnonylic acid, cetyloxybutyn'c acid, cetyloxyacetic acid, chlorstearic acid, etc.

Examples of the polycarboxylic acids are those of the aliphatic series, for example, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, nonanedicarboxylic acid, decanedicarboxylic acids, undecanedicarboxylic acids, and the like.

Examples of unsaturated aliphatic polycarboxylic acids are fumaric, maleic, mesocenic, citraconic, glutonic, itaconic, muconic, aconitic acids, and the like,

Examples of aromatic poly'carboxylic acids are phthalic, isophthalic acids, terephthalic acids, substituted derivatives thereof (e.g., alkyl, chloro, alkoxy, etc. deviratives), biphenyldicarboxylic acid, diphenylether dicarboxylic acids, diphenylsulfone dicarboxylic acids and the like.

Higher aromatic polycarboxylic acids containing more than two carboxylic groups are himimellitic, trimellitic, trimesic, mellophanic, prehnitic, pyromellitic acids, mellitic acid, and the like.

Other polycarboxylic acids are the dimeric, trimeric, and polymeric acids, for example, dilinoleic, trilinoleic, and other polyacids sold by Emery Industries, and the like. Other polycarboxylic acids include those containing ether groups, for example, diglycolic acid. Mixtures of the above acids can 'be advantageously employed.

In addition, acid precursors such as acid anhydrides, esters, acid halides, glycerides, etc., can be employed in place of the free acid.

Examples of acid anhydrides are the alkenyl succinic acid anhydrides.

Any alkenyl succinic acid anhydride or the corresponding acid is utilizable for the production of the reaction products of the present invention. The general structural formulae ofthese compounds are:

Anhydride 0 Add wherein R is an alkenyl radical. The alkenyl radical can be straight-chain or branched-chain; and it can be saturated at the point of unsaturation by the addition of a substance 'which adds to olefinic double bonds, such as hydrogen, sulfur, bromine, chlorine, or iodine. It is obvious, of course, that there must be at least two carbon atoms in the alkenyl radical, but there is no real upper limit to the number of carbon atoms therein. However, it is preferred to use an alkenyl succinic acid anhydride reactant having between about 8 and about 18 carbon atoms per alkenyl radical. Although their use is less desirable, the alkenyl succinic acids also react, in aocord ance with this invention, to produce satisfactory reaction products. It has been found, however, that their use necessitates the removal of water formed during the reaction and also often causes undesirable side reactions to occur to some extent. Nevertheless, the alkenyl suc-- 7.. propenyl succinic acid anhydride; sulfurized propenyl succinic acid anhydride; 'butenyl succinic acid; 2-methylbutenyl succinic acid anhydride; 1,2-dichloropentyl succinic acid anhydride; hexenyl succinic acid 'anhydride; hexyl succinic acid; sulfurized 3-methylpentenyl succinic acid anhydride; 2,3-dimethylbutenyl succinic acid anhydride; 3,3-dimethylbutenyl succinic acid; 1,2-dibromo-2- ethylbutyl succinic acid; heptenyl succinic acid anhydride; 1,2-diiodoocty1 succinic acid; octenyl succinic acid anhydride; 2-methylheptenyl succinic acid anhydride; 4-ethylhexenyl succinic acid; 2-isopropylpentenyl succinic acid anhydride; noneyl succinic acid anhydride; 2-propylhexenyl succinic acid anhydride; decenyl succinic acid; decenyl succinic acid anhydride; 5-methyl-Z-isopropylhexenyl succinic acid anhydride; 1,2-dibromo-2-ethyloctenyl succinic acid anhydride; decyl succinic acid anhydride; undecenyl succinic acid anhydride; 1,2-dichloro-undecyl succinic acid anhydride; 1,2-dichloro-undecyl succinic acid; 3-ethyl-2-tbutylpentenyl succinic acid anhydride; dodecenyl succinic acid anhydride; dodecenyl succinic acid; 2- propylnonenyl succinic acid anhydride; 3-butyloctenyl succinic acid anhydride; tridecenyl succinic acid anhydride; tetradecenyl succinic acid anhydride; hexadecenyl succinic acid anhydride; sulfurized octadecenyl succinic acid; octadecyl succinic acid anhydride; 1,2-dibromo-2- methylpentadeceny-l succinic acid anhydride; S-propylpentadecyl succinic acid anhydride; eicosenyl succinic acid anhydride; 1,Z-dichloro-2-methylnonadecenyl succinic acid anhydride; 2-octyldodecenyl succinic acid; 1,2-

diiodotetracosenyl succinic acid anhydride; hexacosenyl succinic acid; hexacosenyl succinic acid anhydride; and hentriacontenyl succinic acid anhydride.

The methods of preparing the alkenyl succinic acid anhydrides are well known to those familiar with the art. The most feasible method is by the reaction of an olefin with maleic acid anhydride. Since relatively pure olefins are difiicult to obtain, and when thus obtainable, are often too expensive for commercial use, alkenyl succinic acid anhydrides are usually prepared as mixtures by reacting mixtures of olefins with maleic acid anhydride. Such mixtures, as well as relatively pure anhydrides, are ntilizable herein.

In summary, without any intent of limiting the scope of the invention, acylation includes amidification, the formation of the cyclic amidine ring, the formation of acid imides such as might occur when anhydrides such as the alkenylsuccinic acids are reacted, i.e.,

CHrC It wherein P=the polyethyleneimine residue, polymers as might occur when a dicarboxylic acid is reacted intermolecnlarly with polyethyleneimine, cyclization as might occur when a dicarboxylic acid reacts intramolecularly with polyethyleneimine as contrasted to intermolecular reactions, etc. The reaction products may contain other substances. Accordingly, these reaction products are most accurately defined by a definition comprising a recitation of the process by which they are produced. i.e.. by acvlation.

The moles of acylating agent reacted with polyethyleneimine will depend on the number of acylation reactive positions contained therein as well as the number of moles of acylating agent one wishes to incorporate into the polymer. Theoretically one mole of acylating agent can be reacted per amino group on the polyethyleneimine molecule. We have advantageously reacted 1-20 moles of acylating agent per mole of polyethyleneimine 900, but preferably 1l2 moles. Proportionately greater amounts of acylating agent can be employed with polyethyleneimine of higher molecular weight. Thus, with polyethyleneimine 20,000, 1-50 moles of acylating agent can be employed, and with polyethyleneimine 35,000, 1l00 moles can be employed, etc. Optimum acylation will depend on the particular use.

The following examples are illustrative of the preparation of the acylated polyethyleneimine.

The following general procedure is employed in acylating. A xylene suspension of polyethyleneimine, after the removal of water, is mixed with the desired ratio of acid. Heat is then applied. After the removal of the calculated amount of water (1 to 2 equivalents per carboxylic acid group of the acid employed), heating is stopped and the azeotroping agent is evaporated under vacuum. The temperature during the reaction can vary from to 200 C. Where the formation of the cyclic amidine type structure is desired, the maximum temperature is generally ISO-250 C. and more than one mole of water per carboxylic group is removed. The reaction times range from 4 to 24 hours. Here again, the true test of the degree of reaction is the amount of water removed.

Example 1A The reaction is carried out in a 5 liter, 3 necked flask furnished with a stirring device, thermometer, phase separating trap, condenser and heating mantle to 1 mole (900 grams) of polyethyleneimine 900 in an equal weight of xylene, (i.e., 900 grams), 200 grams of lauric acid (1 mole) is added with stirring in about ten minutes. The reaction mixture is then heated gradually to about C. in half an hour and then held at about C. over a period of 3 hours until 19 grams (1.1 mole) of water is collected in the side of the tube. The solvent is then removed with gentle heating under reduced pressure of approximately 20 mm. The product is a dark, viscous, xylene-soluble liquid.

Example 1-A TABLE I.-ACYLATED PRODUCTS OF ETHYLENEIMINE POLY Molecular Weight of Polyethyleneimine (PE) Ratio, Mols of Water Removed Per M01 of Acid Ratio, Mols of Acid Per Mol of PE Ex. Acid Laurie (200) TABLE I.--Continued Molecular Ratio, Mols Weight of Ratio, Mols of Water Ex. Acid Polyethyleneof Acid Per Removed imine (PE) M01 of PE Per M01 of Acid 9-Ar. Alkenyl (C11) 50, 000 6:1 1. 5

Succinie Anhy.

gunaptic Acid 10Az .do 50,000 1:1 1.2

11-111.- Mszeic Anhydride 50, 000 1:1

13-A1- Diglycolic (134) 100, 000 1: 1 1. 0

14-A1. Diphenolic (286). 100,000 2:1 1. l

14Az do 100,000 1:1 1.1

The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

TABLE IA.ACYLATED PRODUCTS OF POLYPROPYL- ENEIMINE Molecular Mols of Acid Mols of Water Exam Weight of Acid Per M01 of Removed ple Polypropyl Polypropyl- Per Mol of eneimine eneimine Acid 15-A1. 500 Stearic (284) 2:1 1. 9 15-111.- 500 do 1:1 1.1 15-Aa 500 Laurie (200) 1 1 0. 9 16-A1. 1, 000 Oleic (2S2) 3: 1 1. 0 16-142-- 1,000 Palmitie (256.4) 1:1 1. 2 16-A3. 1,000 Acetic (60).--. 2:1 1.0 17-A1. 5, 000 Stearic (284) 1:1 2.0 17A2. 5,000 o 3:1 1.3 17-A3 5, 000 Dimeric (600 1 1 1. 5 18-A1. 10, 000 Diglycolic (134) 4:1 0. 9 18A2 10, 000 Diphenolic (286) 2:1 1.0 18-As 10, 000 Naphthenic (330) 1:1 1.0 19-A1. 20, 000 Maggie Anhydride 1: 1 19-Az 20, 000 Nonanoie (158).- 4: 1 3. 2 19-A3 20, 000 Oleie (282) 2:1 2. 1 20A1 40, 000 Myristic (228.4 2: 1 1. 7 20-A2 40, 000 Oleic (282) 3:1 2.8 2OA3 40, 000 Alkenyl (O12) Suc- 1:1

cinic Anhydride (266).

OXYALKYLATION Polyethyleneimine can be oxyalkylated in the conventional manner, for example, by means of an alpha-beta alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, octylene oxide, a higher alkylene oxide, styrene oxide, glycide, methylglycide, etc., or combinations thereof. Depending on the particular application desired, one may combine a large proportion of alkylene oxide, particularly ethylene oxide, propylene oxide, a combination or alternate additions of propylene oxide and ethylene oxide, or smaller proportions thereof in relation to polyethyleneimine. Thus, the molar ratio of alkylene oxide to polyethyleneimine can range Within wide limits, for example, from a 1:1 mole ratio to a ratio of 1000: 1, or higher, but preferably 1 to 200. For example, in demulsification extremely high alkylene oxide ratios are often advantageously employed such as 200300 or more moles of alkylene oxide per mole of polyethyleneimine. On the other hand, for certain applications such as corrosion prevention and use as fuel oil additives, lower ratios of alkylene oxides are advantageously employed, i.e., 1/10-25 moles of alkylene oxide per mole of polyethyleneimine. With higher molecular weight polyethyleneimine, more oxyalkylatable reaction centers are pre- 2 weight percent of the total reactants present).

sent for alkylene oxide addition and very high ratios of alkylene oxide can be added. By proper control, desired hydrophilic or hydrophobic properties are imparted to the composition. As is Well known, oxyalkylation reactions are conducted under a wide variety of conditions, at low or high pressures, at low or high temperatures, in the presence or absence of catalyst, solvent, etc. For instance oxyalkylation reactions can be carried out at temperatures of from 200 C., and pressures of from 10 to 200 p.s.i., and times of from 15 min. to several days. Preferably oxyalkylation reactions are carried out at 80 to 120 C. and 10 to 30 p.s.i. For conditions of oxyalkylation reactions see US. Patent 2,792,369 and other patents mentioned therein.

Oxyalkylation is too Well known to require a full discussion. For purpose of brevity reference is made to Parts 1 and 2 of U.S. Patent No. 2,792,371, dated May 14, 1957, to Dickson in which particular attention is directed to the various patents which describe typical oxyalkylation procedure. Furthermore, manufacturers of alkylene oxides furnish extensive information as to the use of oxides. For example, see the technical bulletin entitled, Ethylene Oxide, which has been disturbed by the Jefferson Chemical Company, Houston, Texas. Note also the extensive bibliography in this bulletin and the large number of patents which deal with oxyalkylation processes.

The symbol employed to designate oxyalkylation is O. Specifically 1-0 represents oxyalkylated polyethyleneimine.

In the following oxyalkylations the reaction vessel employed is a stainless steel autoclave equipped with the usual devices for heating and heat control, a stirrer, inlet and outlet means and the like which are conventional in this type of apparatus. The stirrer is operated at a speed of 250 r.-p.m. Polyethyleneirnine dissolved and/or suspended in an equal weight of xylene is charged into the reactor. The autoclave is sealed, swept with nitrogen, stirring started immediately and heat applied. The tem-' perature is allowed to rise to approximately 100 C. at which time the addition of the alkylene oxide is started and added continuously at such speed as it is absorbed by the reaction mixture. When the rate of oxyalkylation slows down appreciably, which generally occurs after about 15 moles of ethylene oxide are added or after about 10 moles of propylene oxide are added, the reaction vessel is opened and an oxyalkylation catalyst is added (in The catalyst employed in the examples is sodium methylate. Thereupon the autoclave is flushed out as before and oxyalkylation completed. In the case of oxybutylation, oxyoctylation, oxystyrenation, and other oxyalkylations, etc., the catalyst is added at the beginning of the operation.

Example 1-O Using the oxyalkylation apparatus and procedure stated above, the following compounds are prepared: grams (1 mol) of polyethyleneimine 900 in xylene are charged into a stainless steel autoclave, swept with nitrogen, stirring started, and autoclave sealed. The temperature is allowed to rise approximately C. and ethylene oxide is injected continuously until 220 grams (5 mols) total had been added over a one-half hour period. This reaction is exothermic and requires cooling to avoid a rise in temperature after removal of xylene. The reaction mass is transferred to a suitable container. Upon cooling to room temperature, the reaction mass is a dark extremely viscous liquid.

Example 1-O The same procedure as Example 1-0 is used except that 396 grams of ethylene oxide (9 mols) is added to 900 grams (1 mol) of polyethyleneimine 900. This reaction material is a dark viscous liquid at room temperature.

I 1 Example 1-O Example 1O A portion of the reaction mass of Example 1O is transferred to another autoclave and an additional amount of EtO was added. The reaction mass now contains the ratio of 1 mol of polyethyleneimine 900 to 40 mols of EtO.

Example 1O The addition of ethylene oxide to Example 1O is continued until a molar ratio of 1 mol of polyethyleneimine 900 to 75 mols of EtO is reached.

Example 1-0 The addition of ethylene oxide to Example 1O is continued until a molar ratio of 1 mol of polyethyleneimine 90 to 83 mols of E is reached.

Example 1O The addition of ethylene oxide to the Example 1O is continued until a molar ratio of 1 mol of polyethyleneimine 900 to 105 rnols of EtO is reached.

Example 16-0 2,000 grams (0.1 mol) of polyethyleneimine of molecular weight of 20,000 in xylene are charged into a conventional stainless steel autoclave. The temperature is raised to 120 C., the autoclave is flushed with nitrogen and sealed. Then 11.6 grams of propylene oxide (0.2 mol) are added slowly at 120 C. A sample is taken at this point and labeled 16-0 This sample contains two mols of PrO for each mol of polyethyleneimine. It is a dark, pasty solid at room temperature.

Example 16-0 The addition of propylene oxide to 16-0 is continued as follows: The autoclave is opened and grams of sodium Inethylate are added. The autoclave is again purged with nitrogen and sealed. Propylene oxide is added carefully until an additional 23.2 grams have been reacted. A sample is taken at this point and labeled 16- 0 This compound now contains 6 mols of propylene oxide for each mol of polyethyleneimine 20,000.

Example 16-0 The oxypropylation of 16-0 is continued until an additional 52.2 grams of propylene oxide are reacted. A sample is taken at this point and labeled 16O 16O contains mols of propylene oxide for each mol of polyethyleneimine 20,000. At room temperature the product is a dark, pasty solid.

This oxyalkylation is continued to produce examples 16-0 16-0 A summary of oxyalkylated products produced from polyethyleneimines is presented in the following Table II.

The Roman numerals, (I), (II), and (III) besides the moles of oxide added indicate the order of oxide addition (I) first, (II) second and (III) third, etc.

The following abbreviations are also used throughout this application:

EtOEthylene oxide Pro-Propylene oxide BuOButylene oxide TABLE II.OXYALKYLATED PRODUCTS: MOLS OF ALK- YLENE OXIDE/MOL POLYETHYLENEIMINE Mol. Wt. of PE EtO PrO BuO 6 (III) 18 (I) 6 (II) g1 (III) Viscous liquid. Solid.

Do. Viscous liquid.

Solid.

Viscous liquid. Dark, thick 0. Viscous liquid.

Solid. Viscous liquid.

Viscous liquid. Dark, thick Do. Viscous liquid. Solid.

Do. Viscous liquid.

Solid. Viscous liquid.

. Hard 56nd.

Pasty solid. D

charged into the autoclave. Following a nitrogen purge and the addition of 75 grams of sodium methylate, the temperature is raised to 135 C. and 2436 grams of PrO (42 mols) are added. At the completion of this reaction, 440 grams of EtO (10 mols) are added and the reaction allowed to go to completion. The resulting polymer is a dark viscous fluid soluble in an aromatic solvent. Ratio of reactants 1 mole starting material/Pro 42 mols/EtO 10 mols.

Example 2-A O For this example a conventional autoclave equipped to handle alkylene oxides is necessary. 525 grams of 2A (0.1 mol) are charged into the autoclave. The charge is catalyzed with grams of sodium methylate, purged with nitrogen and heated to 150 C. 24.6 grams (0.2 mole) of styrene oxide are added and reacted for four hours with agitation. The resulting product is a dark extremely viscous fluid. Ratio of reactants 1 mole starting material/2 moles EtO.

These reactions and other reactions are summarized in the following table.

TABLE III.OXYALKYLATED, PRIOR AOYLATED POLY- ETHYLENEIMINE: MOLS OF OXIDE PER MOL OF REACTANT Example EtO Physical Property Viscous liquid.

Do. Dark, viscous liquid. Solid. Thick liquid. 0.

The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

TABLE IIIA.OXYALKYLATED. P RIO R ACYLATED POLYPROPYLENEIMINE Example PrO BuO Physical Properties Viscous liquid.

Styrene oxide, 3 mols I 5 (III) 1 (II) 2 (I) Do. 65 (I) D0. Epichlorohydriu, 2 mols 113o. 0. 20-1110; 3 D0.

OXYALKYLATION THEN ACYLATION The prior oxyalkylated polyethyleneimine can he acylated with any of the acylation agents herein disclosed (in contrast to acylation prior to oxyalkylation). Since these reactants also have hydroxy groups, acylation, in

16 addition to reaction with amino groups noted above, also includes esterification.

The method of acylation in this instance is similar to that carried out with polyethyleneimine itself, i.e., dehydration wherein the removal of water is a test of the completion of the reaction.

Example 1-O A One mole of 1-0 (1120 grams) in 500 ml. of Xylene is mixed with three moles of acetic acid (180 grams). The temperature is raised slowly at room temperature. to 130 C. and refluxed gently for one hour. The temperature is then raised to 150-460 C. and heated until 3 moles of water and all of the xylene are stripped off. The dark product is water-soluble.

Example 2O A 0.1 mole of 2-0.; (380 grams) in 400 ml. of Xylene is mixed with 0.1 mole of palmitic acid (25.6 grams) at room temperature. Ratio 1 mole 2-0; to 1 mole of palmitic acid. Vacuum is applied and the temperature is raised slowly until one mole of Water (18 grams) is removed. This product is a dark viscous liquid.

Example 2-O A 0.1 mole of 2-0 (757 grams) is mixed with 500 grams of xylene and heated to 100 C. 0.1 mole of diglycolic acid (13.4 grams) is added slowly to prevent excessive foaming. Ratio 1 mole 2-0 to 1 mole glycolic acid. The temperature is raised to -150 C. and held until one mole of water has evolved. This product is the diglycolic acid fractional ester of 2-O A white precipitate forms during this reaction which can be removed by filtration. Analysis shows the precipitate to be sodium acid diglycollate, a reaction product of the catalyst and diglycolic acid. The filtered product is a dark viscous liquid at room temperature.

Table IV contains examples which further illustrate the invention. The symbol employed to designate oxyalkylated, acylated products is OA.

TABLE IV.-ACYLATED, PRIOR OXYALKYLATED POLYETHYLENEIMINE Mols of Aeylating Agent Per Mol Oxyalkylatcd PE Ratio, Mols of Water Removed to Mols Acylating Agent Employed Example Acylating Physical Agent Properties anhydride. Myristic. Abietic Diglycolic Diphenolic Terephthalic Benzoic The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

TABLE IVA.ACYLATED, PRIO-R OXYALKYLATED POLYPROPYLENEIMINE Mols of Acy- Ratio, Mols of lating Agent Water Re- Example Acylating Per Mol of moved to Mols Physical Agent Oxyalkylated of Acylating Properties Polypropylene- Agent imine Employed 27O A Oleic 2 2 Thick dark liquid. 27O4A Diphenolic 1 1 Pasty solid. 28-O3A.-. Laurie 3 1 Do. 28OsA Acetic... 4 1 Do. 29-O A Naphthe e 1 1 Do. 31-0 1 1"- Stearie 2 2 Do. 32-0411- Tall oil l 1 Do. 37O1A Maleic anhy- 1 D0.

dride. 39-0 11-.- Pa1mitie 2 2 Do. 43-0611. Dimerie 3 1 Waxy sol d. 44-O5A... Diglycolic 1 1 Pasty solid. 45O1A. Myristic 2 1 Do. IS- A- Rieinoleic l 1 Do. 50-O A Abietic.. 2 2 Do. til-04A". Linoleic 1 1 Do. 57-O3A... Nonanoi 1 1 Do. 59-0 11- Lanric 1 1 Waxy solid 62-O2A..-. Diglycolic- 1 1 Do.

HEAT TREATMENT OF OXYALKYLATED PRODUCTS The oxyalkylated products described herein, for example, those shown in-Table II relating to oxyalkylated polyethyleneimine and those in Table 111 relating to oxyalkylated, prior acylated, polyethyleneimine can be heat treated to form useful compositions.

In general, the heat treatment is carried out at ZOO-250 C. Under dehydrating conditions, where reduced pressure and a fast flow of nitrogen is used, lower temperatures can be employed, for example, ISO-200 C.

Water is removed during the reaction, such as by means of a side trap. Nitrogen passing through the reaction mixture and/ or reduced pressure can be used to facilitate water removal.

The exact compositions cannot be depicted by the usual chmeical formulas for the reason that the structures are subject to a wide variation.

The heat treatment is believed to result in the polymerization of these compounds and is efiected by heating same at elevated temperatures, generally in the neighborhood of 200270 C., preferably in the presence of catalysts, such as sodium hydroxide, potassium hydroxide, sodium ethylate, sodium glycera te, or catalysts of the kind commonly employed in the manufacture of superglycerinated fats, calcium chloride, iron and the like. The proportion of catalyst employed may vary from slightly less than 0.1%, in some instances, to over 1% in other instances.

Conditions must be such as to permit the removal of water formed during the process. At times the process can be conducted most readily by permitting part ofthe volatile constitutents to distill, and subsequently subjecting the vapors to condensation. The condensed volatile distillate usually. contains water formed by reaction. The water can be separated from such condensed distillate by any suitable means, for instance, distilling with xylene, so as to carry over the water, and subsequently removing the xylene. The dried condensate is then-returned to the reaction chamber for further use. In some instances, condensation can best be conducted in the presence of a highboiling solvent, which is permitted to distill in such a manner as to remove'the water of reaction. In any event, the speed of reaction and the character of the polymerized product depend not only upon the original reactants themselves, but also on the nature and amount of catalyst employed, on the temperature employed, the time of reaction, and the speed of water removal, i.e., the effectiveness with which the water of reaction is removed from the combining mass. Polymerization can be eifected without the use of catalysts in some instances, but such procedure is generally undesirable, due to the fact that the reaction takes a prolonged period of time, and usually a significantly higher temperature. The use of catalyst such as iron, etc. fosters the reaction.

The following examples are presented to illustrate heat treatment. The symbol used to designate a heat treated oxyalkylated polyethyleneimine is OH and an acylated, oxyalkylated product is AOH. In all examples 500 grams of starting material are employed.

Example 2-O H A conventional glass resin vessel equipped with a stirrer and water trap is used. Five hundred grams of 2-0 are charged into the above resin vessel along with five grams of C'aCl The temperature is raised to 225-250 C. and heated until 57 grams of water (3.2 mole) are evolved. This process takes 7.5 hours of heating. The product is an extremely viscous material at room temperature. However, upon warming slightly this product dissolves easily in water.

Example 19O H The process of the immediately previous example is repeated using 19-0 but substituting sodium methylate for calcium chloride. The product is a dark, viscous, water-soluble material.

Example 15O H The process of Example 2O His repeated using 15-0 but substituting powdered iron for calcium chloride.

TABLE V.HEAT TREATED (1) OXYALKYLATED AND (2) ACYLATED, OXYALKYLATED PO LYETHYLENEIMINE Water Removed Ex. Reaction Catalyst (5 grams) Time in Physical Properties Temp, 0. Hours Grams Mols 250 Iron 74 4. l 8. 0 Dark, viscous liquid. 225 OaCh. 57 3. 2 16.5 D0. 265 Sodium methylate. 36 2. 0 23 Do. C C1 38 2.1 30 Do.

95 5. 3 9. 5 Solid. 32 1. 8 12 Viscous liquid. 40 2. 2 13 Do. 72 4 18 Do. 54 3 24 Do. 5 30 Do. 54 3 16 D0. 36 2 18 Do. 76 4. 2 20 Solid. 54 3 16 Viscous liquid. 63 3. 5 8 Do. 57 3. 2 12 Do. 36 2 14 Do. 38 2. 1 11 D0. 40 2. 2 13 D0. 36 2.0 16 Paste. 40 2. 2 8 Do. 90 5 14 Do. 12A202H- 32 l. 8 18 Do.

The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

, 20 It is preferred to perform the reaction between the alkyl halide reactant and polyethyleneimine in a hydrocarbon solvent under reflux conditions. The aromatic TABLE VA.-HEAT TREATED (DPOXYALKYLATED AND (2) AGYLATED, OXYALKYLATED OLYPROPYLENEIMINE Water Removed Ex. Reaction Catalyst (5 grams) Time in Physical Properties Temp., 0. Hours Grams Mols 32 1. 8 18 Dark, viscous liquid. 40 2. 2 8 Do. 40 2. 2 13 Do. 36 2.0 14 Do. 63 3. 5 8 Do. 76 4. 2 Do. 54 3. 0 16 D0. 54 3.0 24 Pasty. 40 2. 2 13 Viscous liquid. 95 5. 3 9. 5 Do. 36 2. 0 23 D o. 74 4.1 8.0 Do. 32 1.8 18 D0. 90 5. (l 14 D0. 36 2.0 16 D0. 38 2. 1 11 Do. 57 3. 2 12 Paste. 54 3.0 16 Do. 36 2.0 18 Do. 90 5.0 Do. 20AiOaH-. 32 1. 8 12 D0.

ALKYLATION Alkylation relates to the reaction of polyethyleneimine and derivatives thereof with alkylating agents.

Any hydrocarbon halide, e.g., alkyl, alkenyl, cycloalkenyl, aralkyl, etc., halide which contains at least one carbon atom and up to about thirty carbon atoms or more per molecule can be employed to alkylate the products of this invention. It is especially preferred to use alkyl halides having between about one to about eighteen carbon atoms per molecule. The halogen portion of the alkyl halide reactant molecule can be any halogen atom, i.e., chlorine, bromine, fluorine, and iodine. In practice, the alkyl bromides and chlorides are used, due to their greater commercial availability. Non-limiting examples of the alkyl halide reactant are methyl chloride; ethyl chloride; propyl chloride; n-butyl chloride; sec-butyl iodide; -t-butyl fluoride; n-amyl bromide; isoamyl chloride; n-hexyl bromide; n-hexyl iodide; hep-tyl fluoride; Z-ethylhexyl chloride; n-octyl bromide; decyl iodide; dodecyl bromide; 7-ethyl-2 -methyl-undecyl iodide; tetradecyl bromide; hexadecyl bromide; hexadecyl fluoride; heptadecyl chloride; octadecyl bromide; docosyl chloride; tetracosyl iodide; hexacosyl bromide; octacosyl chloride; and triacontyl chloride. In addition, alkenyl halides can also be employed, for example, the alkenyl halides corresponding :to the above examples. In addition, the halide may contain other elements besides carbon and hydrogen as, for example, where dichloroethylether is employed.

The alkyl halides can be chemically pure compounds or of commercial purity. Mixtures of alkyl halides, having carbon chain lengths falling within the range specified hereinbefore, can also be used. Examples of such mixtures are mono-chlorinated wax and mono-chlorinated kerosene. Complete instructions for the preparation of mono-chlorowax have been set forth in United States Patent 2,238,790.

Since the reaction between the alkyl halide reactant and polyethyleneimine is a condensation reaction, or an alkylation reaction, characterized by the elimination of hydrogen halide, the general conditions for such reactions are applicable herein. For certain uses it is preferable to carry out the reaction at temperatures of between about 100 and about 250 C., preferably between about 140 C. and about 200 C., in the presence of a basic material which is capable of reacting with the hydrogen halide to remove it. Such basic materials are, for eX- ample, sodium bicarbonate, sodium carbonate, pyridine, tertiary alkyl amines, alkali or alkaline earth metal hydroxides, and the like.

hydrocarbon solvents of the benzene series are especially preferable. Non-limiting examples of the preferred solvent are benzene, toluene, and xylene. The amount of solvent used is a variable and non-critical factor. It is dependent on the size of the reaction vessel and on the reaction temperature selected. For example, it will be apparent that the amount of solvent used can be so great that the reaction temperature is lowered thereby.

The time of reaction between the alkyl halide reactant and polyethyleneimine is dependent on the weight of the charge, the reaction temperature selected, and the means employed for removing the hydrogen halide from the reaction mixture. In practice, the reaction is continued until no more hydrogen halide is formed. In general, the time of reaction will vary widely, such as between about four and about ten hours.

It can be postulated that the reaction between the alkyl halide reactant and polyethyleneimine results in the formation of products where the alkyl group of the alkyl halide has replaced a hydrogen atom attached to a nitrogen atom. It is also conceivable that alkylation of an alkylene group of polyethyleneimine can occur. However, the exact composition of any given reaction product cannot be predicted. For example, when two moles of butyl bromide are reacted with one mole of polyethyleneimine 900, a mixture of mono-, diand triand higher N-alkylated products can be produced. Likewise, the alkyl groups can be substituted on different nitrogen atoms in diiferent molecules of polyethyleneimme.

Thus, the term Alkylation as employed herein and in the claims include alkenylation, cycloalkenylation, aralkylation, etc., and other hydrocarbonylation as well as alkylation itself.

In general, the following examples are prepared by reacting the alkyl halide with the polyethyleneimine at the desired ratio in the presence of one equivalent of base for each equivalent HCl given off during the reaction. Water formed during the reaction is removed by distillation. Where the presence of the anions, such as chlorine, bromine, etc., is not material and salts and quaternary compounds are desired, base is added.

The following examples are presented to illustrate alkylation of polyethyleneimine.

In these examples, the term mesomer is employed. A mesomer is defined as a repeating radical which, when combined with other mesomers, forms the principal portion of the polymer molecule.

2.1 Thus, the unit l H G C.

H H is the mesomer of polyethyleneimine, since polyethyleneimine may be represented by the formula Example -K 430 grams of polyethyleneimine 50,000, equivalent to mesomeric units of ethyleneimine, in 500 ml. of xylene and 570 grams of sodium carbonate, equivalent to 8 moles, are placed in a reaction vessel equipped with a mechanical stirrer, a thermometer and a reflux condenser take-otf for removal of volatile components. The stirred reactants are heated to about 100 C. whereupon 1140 g. (8 mols) of dichloroethyl ether is started in slowly at such a rate that the temperature of the reaction vessel contents never exceeds 165 C., but preferably stays around 135 C. The reaction is exothermic and 5-6 hours are required to add all the dichloroethyl ether. After all the dichloroethyl ether has been added, the temperature is allowed to drop to about 90100 whereupon reduced pressure is applied to the reaction vessel and all xylene stripped out. The material left in the vessel is a thick brown liquid which solidifies upon cooling to a glassy-solid.

Example 8A The equivalent of 8 mesoremic units, based on polyethyleneimine, of the material 8-1 (Table 1) in 300 g. xylene is placed in a reaction vessel described in the above example for 5-K 340 grams anhydrous sodium carbonate, equivalent to 3.2 moles are added followed by 1.6 moles dimethyl sulfate. The temperature is then brought up to 125 C. and held there for a period of 6-8 hours. Xylene is then removed under reduced temperature and pressure conditions as in the example for 5K The resulting product, a dark amber material, is very viscous at ordinary temperature.

Example 20O HK The equivalent of 10 mesomeric units based on polyethyneneimine of the material 2OO H (Table V) in 300 ml. of xylene and 420 grams sodium bicarbonate, equivalent to 5 moles, are placed in an autoclave equipped with a stirring device, a thermometer and a condenser reflux device which can be closed oil from the autoclave during reactions in which pressures above atmosphere are experienced. The autoclave is closed and heat is applied to bring up the temperature to 120-130 C. at which time 5 mols methyl chloride are added slowly while never allowing pressure to exceed 5 atmospheres pressure. Several hours will be necessary to get all methyl chloride in and pressure inside the vessel down to one atmosphere. At this point the reflux condenser is opened, the temperature is allowed to drop to 90-100 C. and a slight vacuum applied in order to reflux the xylene out of the autoclave. The resulting material is a very viscous amber colored liquid.

The reaction shown in the following table are carried out in a similar manner. Each reaction in the table is carried out in two ways-(l) in the presence of base, as in S-K to yield the alkylation product and (2) in the absence of base to yield the halogen-containing or sulfatecontaining (5K X) products.

The alkylated products of this invention contain primary, secondary, tertiary, and quaternary amino groups. By controlling the amount of alkylation agent employed and the conditions of the reaction, etc., one can control the type and amount of alkylation. For example, by reaction less than the stoichiometric amount of alkylation agent one could preserve the presence of nitrogen-bonded 22 hydrogen present on the molecule and by exhaustive alkylation in the presence of suflicient basic material, one can form more highly alkylated compounds.

The moles of alkylating agent reacted with polyethyleneimine will depend on the number of alkylation reactive positions contained therein as well as the number of moles of alkylating agent one Wishes to incorporate into the molecule. Theoretically, every hydrogen bonded to a nitrogen atom can be alkylated. We have advantageously reacted l-20 moles of alkylation agentper mole of polyethyleneimine 900 but preferably 1-12 moles. With polyethyleneimine 20,000 greater amounts of alkylating agent can be employed, for example 1-50 moles, and with polyethyleneimine 40,000, lmoles, etc. Optimum alkylation will depend on the particular application.

In addition, the alkyl halide may contain functional groups. For example, chloroacetic acid can be reacted with polyethyleneimine to yielda compound containing carboxylic acid groups.

PN-CH COOH, wherein P is the residue of polyethyleneimine.

In addition, polyethyleneimine can be 'alkylated with an alkyl halide such as alkyl chloride and then reacted with chloroacetic acid to yield an alkylated polyethyleneimine containing carboxylic acid groups The symbol employed to designate an alkylated polyethyleneimine is K. Where the product is a salt or a quaternary the symbol is KX. Thus, for example, where no acceptor base is employed anda salt is allowed to form 1-A505K would be 1-A505KX.

TABLE VL-ALKYLATED PRODUCTS Mols Mol. Wt. Alkylating Physical Ex. PE Alkylatiug Agent Agent Per Properties Mesomer Unit Allyl chloride. 0. 2 Viscous liquid. do 0. 7. Do. Benzyl chloride 0.3 Do. .do 0. 8 Solid.

Methyl chloride 0. 3 Viscous liquid; --d0 1. 0 Solid.

Ethylene dichlo- 0.2 Viscous ride. liquid. do 0.5 Do. 0 1,4-diehlorobu- 0.2 Do.

tame-2. .d0 0.5 Do. Dimethyl sulfate. 0. 2. Do. do 0.4 Do. Dodecylhenzene 0. 2 Solid chloride. do 0.5 Do.-

chloride. Butyl chloride- 0. 3 Viscous liquid. do 0.6 Do. Diehlorodiethyl 0. 2 Do.

ether. do 0. 8. .Solid.

Benzyl chlor1de 0. 3 .Viscous liquid. .(10 0.8 Solid.

Ethylene diehlq 0. 2 Viscous ride. liquid. .do 0.8 Do. Methyl chlor1de 0. 3 Do. do 1.0 .Solid.

1,4 xyl1dene chlo- 0.2 Viscous ride. liquid. do 0.2. Do. Dodeceuyl chlo- 0. 2 Solid.

ride. Methyl chloride- 0. 5 Viscous liquid. Benzyl chloride. 0. 4 Solid. Dimethyl sulfate 0.2 Viscous liquid Dichlorodiethyl 0. 4 Do.

ether. 1,4-dlchl orobu- 0. 3 Do.

tene-2.

TABLE VI.Cntinued TABLE VIA.Continued Mols Molecular Mols 01' Physical M01. Wt. Alkylating Physical Weight 01 Alkylating Properties Ex. PE Alkylating Agent Agent Per Properties Example Polypro- Alkylating Agent Agent Per Mesomer pylene- Mesomer Unit imine Unit Benzyl chloride 0.4 Solid. 40, 000 Dimethyl sulfate- 0. 3 Solid. Methyl chloride-.. 0. 7 Do. 40, 000 Ethylene dichlo- 0.7 Do. Ethylene dichld 0.2 Viscous ride.

ride. liquid. 40, 000 Butyl chloride--. 0.2 Do. Benzyl chloride-.. 0. 4 Solid. 40, 000 Allyl chride 0.5 Do. Dimethyl sulfate" 0.2 Viscous 40, 000 Benzyl chloride 0.3 Viscous liquid liquid Dichlorodicthyl 0. 4 olid. AzO4K 40, 000 Methyl chloride 1. 0 olid.

ether. 19A3O1K 40, 000 Ethylene dichlo- 0. 0 Do Methyl chloride." 0.6 Do. ride. Dodecyl benzyl 0.2 Solid. Iii-1130311---. 40, 000 Dichloro pcntane 0. 5 Do. chloride. 15 27O2.AK. 40,000 Dichlorodiethyl 0.2 Do. 1,4 xylylene di- 0. 2 Viscous ether.

hloride. liquid 44O5AK. 40, 000 Dimethyl sulfate. 1. 0 Do. Benzyl chloride. 0.5 Solid. 51O4AK 40, 000 Methyl chloride... 0. 8 Do. Methyl chloride- 0.6 Do. 46-O3HK-.- 40, 000 Allyl chloride- 0.5 Do. Dodieeenyl chlo- 0. 2 D0. A1OzHK 40, 000 Butyl chloride.-- 0.2 Do.

r1 e. Ethylene dichlo- 0.3 Viscous 1 iiljehl b 0 2 liquid. 20

, o uo.

tang-2. In addition to the above examples wherem a base Benzyl chloride-.. 0.4 Solid. a h Dicmomdiethyl 0. 4 acceptor is employed to remove the acid nion s as ether. halogen, sulfate, etc., the above examples are also prepared 12-A,olK Methyl chloride--- 0. 5 Do. re I POAIK oetadecylchlm (12 omittingthe inorganic base from the action me 1 m ride. When th1s 1s done, a halogen containing salt, quaternary, Z-OMKK Y etc is formed Examples where such salts are formed hl di V 14 OBAK Q211 20 ethyl 0 3 5321 Wlll be designated as above except that they W111 contain 32 33- an X designation for example instead of 1O A K they I i; j: 1 will be lO A KX, and instead of 22O AK they will be g g y gzf 22-O AKX, etc. X indicates salt formation. 2233? ALKYLATED THEN ACYLATION 20-O1HK-- Methyl chloride-.. 0.5 Do. z Dlmethylsulfawn The alkylated material prepared above can be further The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

TABLE VIA.ACYLATED PRODUCTS Molecular Mols of Weight of Alkylating Physical 7 Example Polypro- Alkylating Agent Agent Per Properties pylene- Mesomer iminc Unit 500 Allyl chloride 0. 2 Viscous liquid. 500 do 0.7 Do. 500 Benzyl chloride 0. 3 Do. 500 do -1. 0.8 Do. 1,000 Methyl chloride- 0. 7 Do. ,000 do 1.0 Do. 1, 000 Ethylene di- 0. 2 Do.

chloride. 1,000 d0 0.5 Do. 5, 000 1-4-chlorobutene-2. 0. 2 Do. 5,000 do 0.5 Do. 5,000 Dimethyl suliate 0. 2 Do. 5,000 do 0.4 Do. 10, 000 Dodecylbenzene 0. 2 Solid.

chlori e. 10,000 do 0.5 Do. 10, 000 Butyl chloride 0.3 Do. 10,000 do 0.6 Do. 20, 000 Dichlorodiethyl 0. 2 Do.

other 20,000 do 0.8 Do. 20, 000 Benzyl chloride 0. 3 Do. 20,,000 d0 0. 8 Do. 000 Methyl chloride. 0. 3 Do. 40,000 do 0.8 Do. 40, 000 Allyl chloride- 0. 5 Do. 40, 000 Dimethyl sulfate 0. 8 Viscous liquid. 40, 000 Methyl chloride. 0. 3 Do. 40, 000 Ethylene di- 0. 8 Do.

chloride. 40, 000 Dichlorodiethyl 0. 2 Solid.

ether. 40, 000 Benzyl chloride 0. 6 Do. 20-A1K. 40, 000 lfdichzlorobw 0. 3 Do. we 27-0411 40, 000 Dodecenyl chlo- 0. 5 Viscous ride. liquid. 280;K 40, 000 Benzyl chloride- 0. 2 Do. 29-0311 40, 000 1,4 xylylene di- 1. 0 Do.

chloride. 36O4K 40, 000 Dodecyl benzene 0. 8 Do.

chloride.

treated with acylating agent where residual acylatable amino groups are still present on the molecule. The acylation procedure is essentially that described above wherein carboxylic acids react with the alkylated polyethyleneimine under dehydrating conditions to form amides and cyclic amidines. The product depends on the ratio of moles of water removed for each carboxylic acid group, i.e., 1 mole Water/l mole carboxylic essentially amides; more than 1 mole water/1 mole carboxylic acid group, essentially cyclic amidines, such as imidazolines.

Such compounds are illustrated in the following table. The symbol employed to designate alkylated, acylated products is KA and acylated, alkylated, acylated products is AKA.

TABLE VII.-ACYLATED, PRIOR ALKYLA'IED POLY- ETHYLENEIMINE OR DERIVATIVE Ratio, Mols Mols of Water Acylatmg Removed Per Physical Example Acylatlng Agent Agent Per Mole of Properties M01 PE Rcactant Dcriv.

1-K3A.. Laurie--- 4:1 1 Viscous l' 2-K3A- Oleic 1:1 1. 5 l lfg 3-K1A- Palmiti 1 1 1 Do. 4-K4A. Dimeric 0. 5:1 1 Solid. 5-K1A. Nonanoic- 2 1 1 Viscous l" 5-K;A. Ricinoleic 2:1 1 8 l j o f 5K.-4A Snccinie an- 2:1 1 Do.

hydride alkyl ((3-12). 5-K4A Stearic 1:1 1.5 Solid. 6-K:;A Myristic 2:1 1 Viscous 2A4KA 2:1 1 l is 6A4KA 1:1 1 D0. 2O1KA L 2:1 1 Viscous l- 'd l-OqKAm. Oleic 2:1 1.3 1523 1-O HKA Maleic an- 1:1 Solid hydride.

The following table presents specific illustrations of compounds other than polyethyleneimine and its derivatives.

TABLE VIIA.ACYLATED, PRIOR ALKYLATED POLY- PROPYLENEIMINE OR DERIVATIVE Ratio, Mols of Mols of Acylating Acylating Agent Water Physical Example Agent Per M01 of Removed Prop- Polypropylenei- Per Mol of erties mine Derivative Reactant 2:1 1 Viscous liquid 2:1 1 D0. 1:1 1 Do. 2:1 1 Do. 2:1 1.3 Do. Maleio anhy- 1:1 Solid.

dride. Lauric.-.. 4:1 1 Viscous liquid 1: 1 1. 5 Do. 1:1 1 DO. 05:1 1 7 Do. 2:]. 1 D0. -11 mm. 2:1 1.8 Do 19-11303KA.-- Alkyl 2:1 Solid.

44-O5AK4L-.- 1:1 Viscous liquid 46-O3HKA 2:1 1 Do. 20A1O]HKA 1:1 1 D0.

OLBFINATION Olefination relates to the reaction'of polyethyleneimine and derivatives with olefins.

The compositions of this invention, includingpolyethyleneimine itself as well as reaction products thereof containing active hydrogens, can be reacted'with unsaturated compounds, particularly compounds containing activated double bonds, so as to add polyethyleneimine across the double bonds as illustrated herein:

Where the compound contains an-additional active hydrogen, other unsaturatedmolecules can be added to the original molecule for example:

Where one of more active hydrogens are present at another reactive site, the followingreaction could take place:

26 p The reaction is carried out in the conventional manner such as illustrated, for example, in Synthetic Organic Chemistry, Wagner and Zook, (Wiley, 1953), page 673. Non-limiting examples of unsaturated compounds which can be reacted with the polyamine and derivatives 7 thereof including the following-acrylonitrile, acrylic and methacrylic acids and esters, crotonic acid and esters, cinnamic acid and esters, styrene, styrene derivatives and related compounds, butadiene, vinyl ethers, vinyl ketones, maleic esters, vinyl sulfones, etc.

In addition, polyethyleneimine and derivatives thereof containing active hydrogens can be used to prepare telomers of polymer prepared from. vinyl monomers.

The following are examples of olefination. The symbol employed to designate olefination is U and alkylation, olefination KU.

Example 1-U The ole-fination reaction is carried out in the usual glass resin apparatus. Since the reaction is that of a double bond with an active hydrogen, no water is eliminated. The reaction is relatively simple, as shown by the following example:

Charge 900 grams of polyethyleneimine 900 in xylene ('1 mol), into glass resin apparatus. Care should be taken that the PEI 900 is water-free, to eliminate undesirable side reactions. At room temperature, slowly add 53 grams of acrylonitrile (1 mol). The reaction proceeds smoothly without the aid of a catalyst. Warm gently to 80 -100 C. and stir for one hour.

Example 6-U To 1,000 grams of polyethyleneimine 100,000 (0.01 mol) in 300 grams of xylene, add 1.24 grams of divinyl sulfone (0.01 mol) at room temperature. This reaction is exothermic and the ambient temperature is employed.

Example 2O KAU Same reactions as Example 1U except that 1 mol of methyl acrylate is substituted for acrylonitrile and 2-0 KA is substituted for the polyethyleneimine 900. Part of this product is thereupon saponified with sodium hydroxide to form the fatty amino acid salt.

Further examples of the reaction are summarized in the following table:

TABLE VIII.-O LEFINATION Mol. Weight Mols of Example of Polyethyl- Olefin Olefin Time Temp,

eneimine Per Mol 0.

Acrylonitrile. 1: 1 80-100 Methylacrylate- 2: 1 80-100 St ene 3: 1 90 Ethyl cinnamate. 2:1 120 Ethyl crot0nate 2:1 125 Dioctyl rnaleate- 2:1 100 Divinyl sulfone- 1: 1 Styrene 1: 1 90 Lauryl methacrylate. 2: 1 135 Divinyl sulfone 1:1 -100 Methyl methacrylate- 1: 1 80-100 Acrylonitrile 3: 1 80-100 Methylacrylateq 3: 1 80-100 Acrylonitrile- 3: 1 80-100 Styrene 3: 1 Divinyl sulfone- 1: 1 70 Ethyl crotonate. 2: 1 125 Dioctyl maleate 2:1 Styrene 1: 1 90 Divinyl sul fnne 1 1 70 Methylscrylate 1: 1 80-100 Divinyl sulfone 1 :1 70 Styrene 3:1 90 D ethyl maleate 1:1 100 Dioctyl maleate 2:1 100 Ethyl crotonate 2:1 Divinyl sulfone 1:1 70

TABLE VIIL-Continued M01. Weight Mols of Example of Polyethyl- Olefin Olefin Time Temp.,

eneimme Per Mol 0.

Styrene 4:1 1 hr 90 Acrylonitrile- 3: 1 1 hr- 80-100 Methylacrylate.-- 3: 1 1 hr- 80-100 Acrylonitrile 3:1 30 min- 80-100 Methyl methaerylate. 1: 1 1 hr. 80-100 Divinyl sulfone 1: 1 1 hr 70 Lauryl methaerylate 2:1 3 hrs. 135 Divinyl sulfone 1:1 1 hr 70 Dioctyl maleate 2:1 2 hrs 100 Ethyl crtonate- 2:1 3 hrs 125 Ethyl einnamate. 2:1 3 hrs. 120 Styrene 3:1 2 hrs 9O Methylaerylate 2: 1 1 hr- 80100 1-01HKAU- Acrylonitrile 1 :1 1 hr 80-100 The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

TAB LE VIIIA.--O LEFINATION 0F POLYPROPYLENEIMINE Molecular Mols of Weight of Olefin Per Time Temp.,

Example Polypro- Olefin M01 of in C.

pylene- Polypropyl- Hours 1m1ne eneimme 7-U1 500 Styrene 1:1 1 90 7-111- 500 Divinyl sulfone 1 :1 1 70 7-U3- 500 Acrylonitrile 2:1 1 80-100 8U1 1, 000 Dioctyl maleate--. 1:1 2 120 S-Ua 1, 000 Methylacrylateuu 1: 1 1 110 8-113. 1, 000 Ethyl einnamate 3:1 2 125 9-U1 5, 000 Lauryl methae- 1:1 3 130 rylate. 9-Uz- 5, 000 Ethyl crotonate 1: 1 3 120 9-U3 5, 000 Acrylonitrile 4: 1 1 80-100 10-Ur- 10, 000 Styrene 2:1 1 9O IO-Ug 10,000 Divinyl sulione- 1: 1 1 80 10-U3- 10, 000 Methylaerylatenn 2: 1 1 100 11-Ur- 20, 000 Lauryl methac- 1:1 3 110 rylate. ll-Uz- 20, 000 Styrene 2:1 1 9O 1lU3 20, 000 Divinyl sult0no 1: 1 1 80 12-U1- 40, 000 Methyl acrylate 2: 1 2 120 12-11; 40, 000 Acrylonitrile 3: 1 1 80 12-Ua 40, 000 Dioctyl malcate 1:1 4 110 CARBONYLATION Carb onylat1on relates to the reaction of polyethyleneimine and derivatives thereof with aldehydes and ketones.

Where primary amino groups are present on the polyethyleneimine reactants, Schifis bases can be formed on reaction with carbonyl compounds. For example, where an aldehyde such as salicylaldehyde is reacted with polyethyleneimine 900 in a ratio of 2 moles of aldehyde to 1 mole of PE 900, the following type of compound could be formed:

HO OH Lesser molar ratios of aldehyde to polyamine would yield mono-Schitfs base such as etc., and other isomeric configurations, such as where the Schiffs base is present on the non-terminal amino groups rather than on the terminal amino group, etc.

A wide variety of aldehyde may be employed such as aliphatic, aromatic, cycloaliphatic, heterocyclic, etc., including substituted derivatives such as those containing aryloxy, halogen, heterocyclic, amino, nitro, cyano, carboxyl, etc., groups thereof. Non-limiting examples are the following:

ALDEHYDES Benzaldehyde 2-methylbenzaldehyde 3-methylbenzaldehyde 4-methylbenzalde'hyde I Z-methoxybenzaldehyde 4-methoxybenzaldehyde a-naphthaldehyde b-naphthaldehyde 4-phenylbenzaldehyde Propionaldehyde n-Butyraldehyde Heptaldehyde Aldol Z-hydroxybenzaldehyde 2-hydroxy-fiamethylbenzaldehyde 2-hydroxy-3-methoxybenzaldehyde 2-4-dihydroxybenzaldehyde 2-6-dihydroxybenzaldehyde Z-hydroxynaphthaldehyde-1 l-hydroxynaphthaldehyde-Z Anthrol-Z-aldehyded 2-'hydroxyfluorene-aldehyde-1 4 hydroxydiphenyl-aldehyde-3 3-hydroxyphenanthrene-aldehyde-4 1-3-dihydroxy-2-4-dialdehydebenzene 2-hydroxy-S-chlorobenzaldehyde 2-'hydroxy-3 S-dibromobenzaldehyde 2-hydroXy-3anitrobenzaldehyde 2-hydroxy-3-cyanobenzaldehyde 2-hydroxy-3-carboxybenzaldehyde 4-hydroxypyridine-aldehyde-3 4-hydroxyquinoline-aldehyde-3 7-hydroxyquinolineealdehyde-8 Formaldehyde Glyoxal Glyceraldehyde Schifis bases are prepared with the polye-thyleneimines of this invention in a conventional manner such as described in Synthetic Organic Chemistry by Wagner & Zook (1953 Wiley), pages 728-9.

Where more extreme conditions are employed, the products may be more complex wherein the carbonyl reactant instead of reacting intramolecularly in the case of a Schifis base may react intermolecular-1y so as to act as a bridging means between two or more polyethyleneimine compounds, thus increasing the molecular weight of the polyethyleneimine as schematically shown below in the case where formaldehyde is the carbonyl compound:

In addition to increasing the molecular weight by means of aldehydes, these compounds result in the formation of Example 1-C Charge 900 grams of polyethyleneimine 900 and 900 I grams of xylene into a conventional glass resin apparatus fitted with a stirrer, thermometer and side-arm trap. Raise temperature to 90 C. and slowly add 44 grams of acetaldehyde (1 mol). Hold at this temperature for three hours. Vacuum is then applied until all xylene is stripped off. The reaction mass is a thick dark liquid which is soluble in water.

Example -C Using the same apparatus as above, charge 500 g. (0.1 mol) of polyethyleneirnine 5,000. While stirring, add slowly at room temperature 8.2 grams of 37% aqueous formaldehyde (0.1 mol of HCHO). After the reaction has ceased, raise temperature to 100 C. The reaction mass may be stopped at this point. It is a viscous watersoluble material. However, it is possible to continue heating under vacuum until all of the water has been eliminated. Cross-linking occurs with this procedure and care must be taken to prevent insolubilization.

Further examples of this reaction are summarized in the following table:

TABLE IX.CARBONYLATION M01. M01 Ratio Weight Aldehyde Example of Poly- Aldehyde to Poly- Temp., Time ethyleneethylene- C.

imine imine or Deriv.

1C1 900 Acetaldehyde. 1:1 90 3 hours 900 do 2:1 90 Do. 900 .do 3:1 90 Do. 5, 000 Heptaldehyde.- 5:1 125 4 hours 5, 000 do 3:1 125 D0. 1:1 125 Do. 2:1 80 1 hour 1:1 80 Do 0. 5:1 80 Do. 4-C1 6:1 140 3 hours 5:1 140 D0. 3:1 140 D0. 3:1 1 hour 2:1 D0. 2:1 Do. 6:1 125 5 hours.

3:1 125 Do. 100, 000 do 2:1 125 Do. 1.A. C 100, 000 salllicglalde- 3:1 120 2 hours.

y e. 2-A4C 100, 000 do 2:1 120 D0. 4A3C 100, 000 do 1:1 120 Do. 6A4G 100, 000 Benzaldehyde 3:1 110 1 hour 8A3C 100, 000 do 2:1 110 Do. 1-O1C 1:1 110 Do. 2O1 3:1 100 2 hours 3O1C 2:1 100 Do 19-010..- v.do 1:1 100 Do. -O C Formaldehyde 3:1 (3) 1 hour 22-O C..- .-(10 2:1 D0. 1-A50r0 d0 121 (2) D0. 1A O6C Glyceralde- 3: 1 130 4 hours hyde. 6A4OC -110 2:1 130 D0. 12O AC Flllllfilalde- 3:1 100 1 hour 2:1 100 Do. 1:1 100 Do. 3:1 140 6 hours 2:1 140 Do. 1:1 140 D0. 3:1 1 hour 2:1 (2) Do. 1:1 (2) D0.

1 Start at 0., raise to 100 C. 2 Start 25 C., raise to 90 C.

The following table present-s specific illustration of compounds other than polyethyleneimine and its derivatives.

TABLE IXA.CARBONYLATION Mol Ratio Aldehyde Temp, to Poly- C. propyleneimine Molecular Weight of Polypropyleneunine Time Example Aldehyde in Hours Beuzaldehyde. do

- -do Salicylalde- Formalde- Glyceraldehyde. Heptaldehyde. Futfuralde- Formaldehyde. Amati-aldehyde- 20AiO2KAC 7-UzC 12-UaC 1 Start at 25 0., raise to C.

The examples presented above are non limitingexamples. It should be clearly understood that various other combinations, order of reactions, reaction ratios, multiplicity of additions, etc., can be employed. Where additional reactive groups are still present on the molecule, the reaction can be repeated with either the original reactant or another reactant.

The type of compound prepared is. evident from the letters assigned to the examples. Thus, taking the branched polyamine as the starting material, the following example designations have the following meaning:

Example designation: Meaning (1) A Acylated.

(2) A0 Acylated, thenoxyalkylated.

(3) AOA Acylated, then oxyal'kylatedthen \acrylated.

(4') AOH Acylaited, then oxyalkylated, then heat treated.

(5) AX Salt or quaternary of (1).

(6) AOX Salt or quaternary of (2).

(7) AOAX Salt or quaternary of '(3).

(8) AOHX Salt or quaternary of (4).

(9) -O Oxyalkylated.

(10) 0A Oxyalkylated,.then acylated.

(11) OH Oxyalkylated, then heat treated.

(12) K Al-kylated.

(13) KX Salt or quaternary of (12).

(14) KA Alkylated, then acylated.

(15) AK Acylated, then alkylated.

(16) AKX Salt or quaternary of ('15).

(17) OK 'Oxyalkyl-ated, then alkylated.

(13) OKX 'Saltor quaternary of (17).

(19) C Carbonylated.

(20) AC Acylated, then caribonylated.

Example designation: Meaning (2-1) KC Alkylated, then carbonyl-ated. (22) CO Carbonylated, then oxyalkylated. (23) -U Olefinated.

(24) AU Acylated, then olefinated. (25) KU Alkylated, then olefinated. (26) KUX Salt or quaternary of (25).

In addition to polyethyleneimine itself, other polyalkyleneim-ines can be employed, a typical example of which is polypropyleneimines. Propyleneimine is now commercially available and can be polymerized to the polymer and polypropyleneim-ine can then be reacted in a manner similar to those reactions shown above. Thus, the teachings contained herein also apply to other polyalkyleneimines besides polyethyleneimine and derivatives thereof.

ASPHALT ANTI-STRIP ADDITIVES This phase of the invention relates to the use of the compounds of our invention in securing a satisfactory bond between bituminous compositions and the various surfaces tov which they are applied in industrial operations, such as road-building. This problem is well-recognized, and many attempts have been made to overcome it. For example, see US. Patents Nos. 2,317,959, dated April 27, 1943, to Johnson et al; 2,361,488, dated October 31, 1944, to Mikeshka; 2,386,867, dated October 16, 1945, to Johnson; 2,508,428-9, dated May 23, 1950, to Smith et al.

In road-construction use, bituminous compositions are employed in conjunction with various mineral materials, sometimes mineral materials like cinders or slags, but more usually of natural origin, such as sand, rock, etc. It is obvious that the potentially usable aggregates include all the various kinds of rock native to the localities where roads are to be built. For example, limestone, dolomite, silica, rhyolite, caliche, and sedimentary, metamorphic, or igneous rocks of various other kinds, are regularly used in road-building. Such mineral aggregates are .hydropihilic in character, a fact that is generally considered to be principally responsible for the existence of the bitumen-stripping problem.

When a bituminous substance such as asphalt, in molten, cutback, or emulsified form, is applied to such hydrophilic surfaces as those of mineral aggregates (in roadbuilding), concrete Walls (in water-proofing), paper (in water-proofing), etc., it is difficult to secure prompt coating of .the surfaces by the bituminous material. Further, it is difiicult to prevent the stripping or removal of such bituminous coating from such surfaces, with time. Prevention of stripping is the more important consideration, although ease of application is frequently of material importance.

Where the surface is moist, damp, or actually soaked, the problem is obviously intensified, because the bitumen must not, only coat the surface, but it must first dislodge a tenaciously held water film. Some aggregates are river gravels; when freshly-dredged they come to the job saturated with water. Rainstonms occurring during construction also produce soaked aggregates and promote stripping. Some aggregates, like caliche, and some limestonesa-nd dolomites are quite porous and retain considerable "water in the interstices after the outer surfaces of the particles seem reasonably dry.

Insorne cases it has been necessary first to dry the surface before applying the bituminous coating. Roadways Jaid in wet weather deteriorate rapidly in use. Where a bituminous roadway is subjected to water, as in low-lying areas or areas where water run-off is frequent or constant, it soon disintegrates, with the development of holes. The aggregate used in its construction is easily broken down to individual pebbles or small clumps of pebbles under such conditions, in absence of some corrective or preventive procedure, such as drying the aggregate by heat, before use,

I Bituminous compositions which include our reagents resist stripping from the surfaces to which they are applied. In other words, they are strip-resistant, as compared with the same bitumen used in absence of our reagents.

Where the bituminous composition is to be used for water-proofing walls or paper or other surfaces, the mixture of it with our reagent is the finished or complete composition.

Within the terms bitumen, bituminous compositions, bituminous materials, and similar expressions including the word bituminous, we mean to include natural asphalt, petroleum still residues of paving grade, plastic residues from coal tar distillation, petroleum pitch, solutions of such substances like cut-back asphalts, emulsions thereof, and the like.

To accomplish the foregoing objectives, the agents of our invention are required to be employed in only very small proportions, generally not more than 1% by weight of such reagents based on the weight of the bituminous component, but preferably 0.1% to 0.8%, being sufficient satisfactorily .to control stripping. However, larger amounts may be employed if desired. 7

While our reagents are highly effective when used in absence of other available additives, they are useful in conjunction with, or admixed with, any other effective and compatible anti-stripper. For example, US. Patent No. 2,392,863, dated January 15, 1946, to Rudd, claims tall oil as an anti-stripper. Our reagents are generally compatible with tall oil, and are used for their present purpose in the presence of tall oil, or can be applied in the form of an admixture with tall oil.

Ordinarily, our reagents are added to or incorporated in the bituminous component before it is incorporated into any mixture. For example, they are added to molten asphalt or to cutback asphalt. If desired, our reagents are added to the mixer in which the bituminous material and the mineral aggregate are being mixed. In the case of bituminous emulsions, our reagents are added to the emulsion after it has been produced or to the bituminous component of such emulsions, before emulsification. The procedure of incorporating our reagents is not critical; the important thing is that they be as uniformly distributed throughout the finished composition as is possible.

For various reasons, including viscosity, we prefer to employ our reagents in the form of a solution in a suitable solvent. In some instances, especially Where salt forms of our reagents are desired or required, water is the solvent selected, because of cost considerations. Where the reagent is water-insoluble or where water is unacceptable as a solvent, for temperature or other reasons, various organic solvents are employed. Aromatic petroleum solvent, sulfur dioxide extract, and petroleum distillates of various kinds, are useful. The solvent is not a material part of our invention. Any suitable solvent may be employed; usually the selection will be on the basis of cost. We prefer aromatic petroleum solvent because of its good solvent power and low cost. When our preferred reagents, described above, are mixed with aromatic petroleum solvent in equal volumes, a solution of satisfactory viscosity is produced. It is the preferred form of employing reagents. Our reagents are often added to asphalt, for example, at the refinery. This is a desirable procedure where large volumes are to be handled or where the asphalt is so heavy-bodied as to require heat- 33 ing to insure uniform distribution of the anti-stripper. Where conditions in the field are such that adequate mixing is achieved, our reagents are often added there, as the asphalt is used. Reagents appear to be quite stable at the usual storage and working temperatures of asphalt.

If the reagent is added at the refinery, the following examples of procedure is practicable: Place the bituminous material or asphalt in a tank containing heating coils and bring it to a temperature at which its viscosity is relatively low. Add 1 pound of our reagents (in the form of a 50 weight percent solution in aromatic petroleum solvent) to every 133 pounds of bitumen, a ratio of 0.75%. If the asphalt is SC-6 or penetration grade asphalt, considerable heating will be required to bring the asphalt to acceptable fluid state. Pour in the desired proportion of reagent and mix it in the asphalt by rolling with gas, recycling through a mixing tank with mixingtype pumps, or stirring with a propeller or other tank-type stirrer. The bituminous mixture so prepared is delivered to the job ready for use in any desired method of application.

There may be, for example, direct application by spraying it on already-laid aggregate; application to a continuous road-mixing unit; or addition to a hot-mix plant. The reagent-asphalt mixture may be sprayed or poured for seal-coat application in the conventional manner. The presence of the reagent does not adversely affect the properties of the asphalt, or the application of the latter; the

' bituminous material is handled exactly as if no reagent had been added.

Where small batches of several-barrel size are involved, addition of the reagent may take place in the field, followed by hand stirring until a uniform distribution of reagent has been achieved.

Where the reagent is to be incorporated in an emulsified bituminous composition, it may be added to the bitumen ingredient in the manner just described; or it may be added to the finished emulsion by simply stirring it in the desired proportion in any conventional manner. The salt form of the reagent may be preferable in such latter instances. We have added our compounds in 50 weight percent solution in aromatic petroleum solvent to emulsified asphalt to produce a highly strip-resistant composition.

If desired, our reagents are added to and mixed with the aggregate before it is coated with the bituminous composition. While this is a less common procedure, it is perfectly feasible, especially where the reagent is sufficiently water-dispersible to give a reasonably stable dispersion which can be quite uniformly distributed through-' out the aggregate.

A number of laboratory techniques have been proposed to evaluate anti-strippers. All or nearly all of them include the operation of coating sornc surface with a bituminous composition, subjecting the coated surface to stripping conditions, and appraising the degree of stripping that has taken place. Our reagents demonstrate their effectiveness strikingly in such tests.

One such test (Test #1) subjects a measured amount of mineral aggregate to a measured amount of water; thereafter coats the aggregate with the bitumen or bitumen-additive mixture; cures or ages the coated sample for a definite period of time; then strips the coated aggregate with water at a definite temperature and for a definite time; and thereafter, usually by visual examination, determines the precentage of the aggregate particles that have been stripped of their original bituminous coating.

The following examples are presented to illustrate this phase of the present invention:

The anti-stripping agents are tested according to the general procedure of Test #1, described above, by mixing 0.5% by weight of the anti-stripping agents listed in the table below into a MC-3 asphalt heated to about 200275 F. This asphalt mixture is then used to coat a wet rock aggregate containing about 2% by weight of 34 water (San Gabriel #4 crushed). (as well as a control containing no anti-stripping agent) is then aged for 20 hours at room temperature. At the end of this time water (3 times the weight of the coated aggregate) is added and this mixture is stirred for 5 min utes at 150-175 F. Thereupon the coated'aggregates are examined to determine the percentage of the aggregates that have been stripped of their asphalt coating.v

Similar effects are achieved with asphalt emulsions. In

' all cases aggregates containing the composition shown in the following table are superior to the control.

ASPHALT ANTI-STRIP ADDITIVES Molecular wt.

Polyethyleneimine 900 Polyethyleneimine 5,000 Polyethyleneimine 11,500 Polyethyleneimine 20,000 Polyethyleneimine 50,000 Polyethyleneimine 100,000

10-A 4-K X 12-A O 1-O KA ASPHALT ANTI-STRIP ADDITlVE-S Molecular wt.

1. A strip-resistant bituminous composition containing a major amount of a material containing a major proportion of a bituminous component and a minor amount, sufficient to inhibit stripping of said material from surfaces to which it may be applied, of a compound selected from the group consisting of (1) a linear polymer of a 1,2-alkyleneirnine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms, (2) an acylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms, formed by reacting, at a temperature of from about 120 C. to about 300 C., said linear polymer with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, (3) an oxyalkylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms,

formed 'by reacting, at a temperature of from about C. to about 200 C. and a pressure of from about 10 p.s.i. to about 200 p.s.i., said polymer with an alkylene oxide having at least 2 carbon atoms, (4) an alkylated linear polymer of a 1,2-alkyleneimine, said polymer hav- The coated aggregate" 35 ing a molecular weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms, formed by reacting, at a temperature of from about 100 C. to about 250 C., said polymer with a hydrocarbon halide alkylating agent having 1 to 30 carbon atoms, (5) an olefinated linear polymer of a 1,2alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms, formed by reacting, at a temperature of from about 70 C. to about 100 C., said polymer with an olefinating agent selected from the group consisting of acrylonitrile, styrene, butadiene, vinyl ethers, and vinyl sulfones, (6) a Schiff base reaction product of a linear polymer of 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms, formed by reacting said polymer with a compound selected from the group consisting of aldehydes and ketones, (7) an acylated, then oxyalkylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2-20 carbon atoms, formed by reacting, at a temperature of from about 125 C. to about 300 C., said linear polymer With an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, and then reacting said acylated polymer, at a temperature of from about 80 C. to about 200 C. and a pressure of from about p.s.i. to about 200 p.s.i., with an alkylene oxide having at least 2 carbon atoms, (8) an oxyalkylated, then acylated linear polymer of a 1,2alkyleneimine, said polymer having a molecular weight of at least 800, said alkylene unit therein having 2-20 carbon atoms, formed by reacting, at a temperature of from about 80 C. to about 200 C. and a pressure of from about 10 p.s.i. to about 200 p.s.i., said polymer with an alkylene oxide having at least 2 carbon atoms and then reacting said oxyalkylated polymer, at a temperature of from about 120 C. to about 300 C., with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, (9) an alkylated, then acylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 220 carbon atoms, formed by reacting, at a temperature of from about 100 C. to about 250 C., said polymer with a hydrocarbon halide alkylating agent having l-30 carbon atoms, and then reacting said alkylated polymer, at a temperature of from about 120 C. to about 300 C., with an acylating agent selected from the group consisting of (i) a carboxylic acid having 739 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, (10) an acylated, then alkylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight-of at least 800, each alkylene unit therein having 2-20 carbon atoms, formed by reacting, at a temperature of from about 120 C. to about 300 C., said polymer with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, and then reacting said acylated polymer, at a temperature of from about 100 C. to about 250 C., with ahydrocarbon halide alkylating agent having 1-30 carbon atoms, (11) an oxyalkylated, then alkylated linear polymer of a 1,2- alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2-20 carbon atoms, formed by reacting, at a temperature of from about 80 C. to about 200 C. and a pressure of from about 10 p.s.i. to about 200 p.s.i., said polymer with an alkylene oxide having at least 2 carbon atoms, and then reacting said oxyalkylated polymer, at a temperature of from about 100 C. to about 250 C., with a hydrocarbon halide alkylating agent having l-30 carbon atoms, (12) a Schiff base reaction product of an acylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2-20 carbon atoms, formed by reacting, at a temperature of from about 120 C. to about 300 C., said polymer with an acylatrng agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, and then reacting said acylated polymer with a compound selected from the group consisting of aldehydes and ketones, (13) a Schiff base reaction product of an alkylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2-20 carbon atoms, formed by reacting, at a temperature of from about 100 C. to about 250 C., said polymer with a hydrocarbon halide alkylating agent having l-30 carbon atoms, and then reacting said alkylated polymer with a compound selected from the group consisting of aldehydes and ketones, (14) an oxyalkylated Schiff base reaction product of a linear polymer of a 1,2-alkyleneirnine, said linear polymer having a molecular weight of at least 800, each alkylene unit therein having 2-20 carbon atoms formed by reacting said linear polymer with a compound selected from the group consisting of aldehydes and ketones to form said Schilf base reaction product and then reacting said Schiff base reaction product, at a temperature of from about C. to about 200 C. and a pressure of from about 10 p.s.i. to about 200 p.s.i., with an alkylene oxide having at least 2 carbon atoms, (15) an acylated, then olefinated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2-20 carbon atoms, formed by reacting, at a temperature of from about 120 C. to about 300 C., said linear polymer with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, and then reacting said acylated polymer, at a temperature of from about 70 C. to about C., with an olefinating agent selected from the group consisting of acrylonitrile, styrene, butadiene, vinyl ethers and vinyl sulfones, and (16) an alkylated, then olefinated linear polymer of a 1,2-allryleneirnine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 220 carbon atoms, formed by reacting, at a temperature of from about 100 C. to about 250 C., said polymer with a hydrocarbon halide alkylating agent having from 1-30 carbon atoms, and then reacting said alkylated polymer, at a temperature of from about 70 C. to about 100 C., with an olefinating agent selected from the group consisting of acrylonitrile, styrene, butadiene, vinyl ethers and vinyl sulfones.

2. The strip-resistant bituminous composition of claim 1 wherein the linear polymer of a 1,2-alkyleneimine is a polyethyleneimine.

3. The strip-resistant bituminous composition of claim 1 wherein the linear polymer of 1,2-alkyleneimiue is a polypropyleneimine.

References Cited by the Examiner UNITED STATES PATENTS 2,182,306 12/1939 Ulrich. 2,272,489 2/ 1942 Ulrich. 2,679,462 5/1954 M-onson l06273 XR 2,945,863 7/1960 Buc et al. l06273 XR 3,060,210 10/1962 De Groote et al. l06281 XR ALEXANDER H. BRODMERKEL, Primary Examiner. LESLIE H. GASTON, Examiner.

I. B. EVANS, Assistant Examiner. 

1. A STRIP-RESISTANT BITUMINOUS COMPOSITION CONTAINING A MAJOR AMOUNT OF A MATERIAL CONTAINING A MAJOR PROPORTION OF A BITUMINOUS CONPONENT AND A MINOR AMOUNT, SUFFICIENT TO INHIBIT STRIPPING OF SAID MATERIAL FROM SURFACES TO WHICH TO MAY BE APPLIED, OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF (1) A LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2 TO 20 CARBON ATOMS, (2) AN ACYLATED LINEAR POLYMER OF A 1,2-ALKYLENEINMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2 TO 20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE TURE OF FROM ABOUT 120*C. TO ABOUT 300*C., SAID LINEAR POLYMER WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRECURSOR OF SAID CARBOXYIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, (3) AN OXYALKYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2 TO 20 CARBON ATOMS, FOMRED BY REACTING AT A TEMPERATURE OF FROM ABOUT 80*C TO ABOUT 200*C. AND A PRESSURE OF FROM ABOUT 10 P.S.I. TO ABOUT 200 P.S.I., SAID POLYMER WITH AN ALKYLENE OXIDE HAVING AT LEAST 2 CARBON ATOMS, (4) AN ALKYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMERD HAVVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2 TO 20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 100*C. TO ABOUT 250*C., SAID POLYMER WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING 1 TO 30 CARBON ATOMS, (5) AN OLEFINATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2 TO 20 CARBON ATOMS FORMED BY REACTING AT A TEMPERATURE OF FROM ABOUT 70*C. TO ABOUT 100*C., SAID POLYMER WITH AN OLEFINATING AGENT SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE, STYRENE, BUTADIENE, VINYL ETHERS, AND VINYL SULFONES, (6) A SCHIFF BASE REACTION PRODUCT OF A LINEAR POLYMER OF 1,2-ALKYLENEMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2 TO 20 CARBON ATOMS, FORMED BY REACTING SAID POLYMER WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALDEHYDES AND KETONES, (7) AN ACYLATED, THEN OXYALKYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING AT A TEMPERATURE OF FROM ABOUT 125*C. TO ABOUT 300*C., SAID LINEAR POLYMER WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, AND THEN REACTING SAID ACYLATED POLYMER, AT A TEMPERATURE OF FROM ABOUT 80*C, TO ABOUT 200* C. AND A PRESSURE OF FROM ABOUT 10 P.S.I. TO ABOUT 200 P.S.I., WITH AN ALKYLENE OXIDE HAVING AT LEAST 2 CARBON ATOMS, (8) AND OXYALKYLATED, THEN ACYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, SAID AKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 80*C. TO ABOUT 200*C. AND A PRESSURE OF FROM ABOUT 10 P.S.I. TO ABOUT 200 P.S.I., SAID POLYMER WITH AN ALKYENE OXIDE HAVING AT LEAST 2 CARBON ATOMS AND THEN REACTING SAID OXYALKYLATED POLYMER, AT A TEMPERATURE OF FROM ABOUT 120*C. TO ABOUT 300*C., WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (Ii) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, (9) AND ALKYLATED, THEN ACYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS FORMED BY REACTING AT A TEMPERATURE OF FROM ABOUT 100*C. TO ABOUT 250*C., SAID POLYMER WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING 1-30 CARBON ATOMS, AND THEN REACTING SAID ALKYLATED POLYMER, AT A TEMPERATURE OF FROM ABOUT 120*C. TO ABOUT 300*C., WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRESURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, (10) AN ACYLATED, THEN ALKYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING AT A TEMPERATURE OF FROM ABOUT 120*C. TO ABOUT 300*C., SAID POLYMER WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, AND THEN REACTING SAID ACYLATED POLYMER, AT A TEMPERATURE OF FROM ABOUT 100*C. TO ABOUT 250*C., WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING 1-30 CARBON ATOMS, (11) AN OXYALKYLATED, THEN ALKYLATED LINEAR POLYMER OF A 1,2ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 80*C. TO ABOUT 200*C. AND A PRESSURE OF FROM ABOUT 10 P.S.I. TO ABOUT 200 P.S.I., SAID POLYMER WITH AN ALKYLENE OXIDE HAVING AT LEAST 2 CARBON ATOMS, AND THEN REACTING SAID OXYLKYLATED POLYMER, AT A TEMPERATURE OF FROM ABOUT 100*C. TO ABOUT 250*C., WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING 1-30 CARBON ATOMS, (12) A SCHIFF BASE REACTION PRODUCT OF AN ACYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 120*C, TO ABOUT 300*C., SAID POLYMER WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRESURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, AND THEN REACTING SAID ACYLATED POLYMER WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALDEHYDES AND KETONES, (13) A SCHIFF REACTION PRODUCT OF AND ALKYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 100*C TO ABOUT 250*C. SAID POLYMER WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING 1-30 CARBON ATOMS, AND THEN REACTING SAID ALKYLATED POLYMER WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALDEHYDES AND KETONES, (14) AN OXALKYLATED SCHIFF BASE REACTION PRODUCT OF A LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID LINEAR POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS FORMED BY REACTING SAID LINEAR POLYMER WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALDEHYDES AND KETONES TO FORM SAID SCHIFF BASE REACTION PRODUCT AND THEN REACTING SAID SCHIFF BASE REACTION PRODUCT AND TEMPERATURE OF FROM ABOUT 80*C. TO ABOUT 200*C. AND A PRESSURE OF FROM ABOUT 10 P.S.I. TO ABOUT 200 P.S.I., WITH AN ALKYLENE OXIDE HAVING AT LEAST 2 CARBON ATOMS (15) AN ACYLATED, THEN OLEFINATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BE REACTING AT A TEMPERATURE OF FROM ABOUT 120*C. TO ABOUT 300*C., SAID LINEAR POLYMER WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRESURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, AND THEN REACTING SAID ACYLATED POLYMER, AT A TEMPERATURE OF FROM ABOUT 70*C. TO ABOUT 100*C., WITH AN OLEFINATING AGENT SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE, STYRENE, BUTADIENE, VINYL ETHERS AND VINYL SULFONES, AND (16) AN ALKYLATED, THEN OLEFINATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, 